Polymer composition

Abstract

To provide: a polymer composition which has excellent oil resistance and is capable of forming a cosmetic or the like that causes no smudging and no powder flaking during use; a method of preparing the same; and a film-forming agent, a cosmetic or the like manufactured using the polymer composition.SOLUTION: A polymer composition comprises: a polymer comprising polymerization units of a first monomer whose homopolymer has a solubility parameter of 11.0 (cal / cm3)1 / 2 or more and a second monomer whose homopolymer has a solubility parameter of less than 11.0(cal / cm3)1 / 2, where the percentage of the polymerization units of the first monomer in the polymer is in the range of 1-40 wt.%, and where the polymer comprises the polymerization units of the second monomer in an amount of 150 to 4000 pts.wt. relative to 100 pts.wt. of the polymerization units of the first monomer.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] This application claims priority based on Korean Patent Application Nos. 10-2019-0133543 and 10-2019-0133542, filed on October 25, 2019, the contents of which are incorporated herein by reference.

[0002] The present application relates to a polymeric composition, a film former, a cosmetic composition or a method for making a polymeric composition. [Background technology]

[0003] Functional polymers are sometimes required for the manufacture of cosmetics, medicines, etc. For example, functional polymers are required for the manufacture of cosmetics and medicines that are applied directly to the skin, including mascara.

[0004] Such functional polymers are required to have oil resistance, i.e. resistance to oily components such as sebum, as well as suitable coatability and film-forming ability.

[0005] In addition, the functional polymer is required to prevent the phenomenon of cosmetics or medicines from bleeding due to sebum, tears, sweat, etc., and from turning into powder and falling off during use.

[0006] Furthermore, cosmetics, medicines, and other products must not contain any harmful substances because they are often used in direct contact with the human body. Summary of the Invention [Problem to be solved by the invention]

[0007] The present application provides a polymer composition, a film former, a cosmetic composition, or a method for manufacturing the polymer composition. The present application aims to provide a polymer composition capable of forming cosmetics that have excellent oil resistance and do not bleed or fall off during use, and a film former or cosmetic manufactured using the same. [Means for solving the problem]

[0008] The polymer composition of the present application may comprise only the polymer described below, or may comprise the polymer described below and other components.

[0009] For example, the ratio of the polymer described below in the polymer composition may be about 5% by weight or more, 10% by weight or more, 15% by weight or more, 20% by weight or more, 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, 90% by weight or more, or 95% by weight or more. Since the polymer composition may consist of only the polymer, the ratio of the polymer may be about 100% by weight or less, 99% by weight or less, or 98% by weight or less. When the components are dispersed or dissolved in a solvent to prepare the polymer composition, the ratio of the polymer is calculated excluding the weight of the solvent.

[0010] The polymer contained in the polymer composition may contain polymerized units of a specific type of monomer, and the ratio of the polymerized units may be adjusted. By controlling the type and ratio of the monomer, it is possible to obtain a polymer composition that can form a film-forming agent, cosmetic, or pharmaceutical product having desired properties, such as oil resistance and preventing bleeding or powdering during use.

[0011] The percentage of a certain monomer referred to in this specification (e.g., weight % or parts by weight, etc.) means the percentage of the monomer applied during the production of the polymer, or the percentage of polymerized units of the monomer contained in the polymer.

[0012] The polymer has a solubility parameter of 11 (cal / cm 3 ) 1 / 2 The polymerization unit of the first monomer is equal to or greater than 11 (cal / cm 3 ) 1 / 2 may include polymerized units of a second monomer that is less than

[0013] In this specification, a polymerized unit of a certain monomer or compound means a form in which the monomer or compound is included as a monomer unit in a polymer through a polymerization reaction.

[0014] The term solubility parameter refers to the solubility parameter of a homopolymer produced by polymerizing the monomer, and the degree of hydrophilicity and hydrophobicity of the monomer can be understood thereby. The method of determining the solubility parameter is not particularly limited and can be according to a method known in the art. For example, the solubility parameter can be calculated or determined according to a method known in the art, known as the Method of Hoftyzer and Van Krevelen, a group contribution.

[0015] The first monomer is a monomer having a relatively hydrophilic property with respect to the second monomer, which can contribute to ensuring the desired oil resistance. In another example, the solubility parameter of the first monomer is 11.5 (cal / cm 3 ) 1 / 2 Above, 12(cal / cm 3 ) 1 / 2 Above, 12.5(cal / cm 3 ) 1 / 2 Above, 13(cal / cm 3 ) 1 / 2 Above, 13.5(cal / cm 3 ) 1 / 2 or more than 14(cal / cm 3 ) 1 / 2 or more, and 20 (cal / cm 3 ) 1 / 2 Below, 19(cal / cm 3 ) 1 / 2 Below, 18(cal / cm 3 ) 1 / 2 Below, 17(cal / cm 3 ) 1 / 2 Below, 16(cal / cm 3 ) 1 / 2 Below, 15(cal / cm 3 ) 1 / 2 Below, 14(cal / cm3 ) 1 / 2 Below, 13(cal / cm 3 ) 1 / 2 Less than or equal to 12.5 (cal / cm 3 ) 1 / 2 It may be about the same or less.

[0016] The first monomer may be a monomer appropriately selected from monomers known to have the above-mentioned solubility parameters.

[0017] For example, the first monomer may have a glass transition temperature (hereinafter, Tg) in the range of −40° C. to 400° C. The Tg of a monomer referred to in this specification is the Tg known for a homopolymer made from the monomer.

[0018] In other examples, the Tg of the first monomer may be -35°C or higher, -30°C or higher, -25°C or higher, -20°C or higher, -15°C or higher, -10°C or higher, -5°C or higher, 0°C or higher, 10°C or higher, 20°C or higher, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 130°C or higher, 140°C or higher, 150°C or higher, 160°C or higher, 170°C or higher, 180°C or higher, 190°C or higher, 200°C or higher, or 210°C or higher, and may be 390°C or lower, 380°C or lower, 370°C or lower, 360°C or lower, 350°C or lower, 340°C or higher, or 350°C or higher. ℃ or less, 330℃ or less, 320℃ or less, 310℃ or less, 300℃ or less, 290℃ or less, 280℃ or less, 270℃ or less, 260℃ or less, 250℃ or less, 240℃ or less, 230℃ or less, 220℃ or less, 210℃ or less, 200℃ or less, 190℃ or less, 180℃ or less, 170℃ or less, 160℃ or less, 150℃ or less, 140℃ or less, 130℃ or less, 120℃ or less, 110℃ or less, 100℃ or less, 90℃ or less, 80℃ or less, 70℃ or less, 60℃ or less, 50℃ or less, 40℃ or less, 30℃ or less, 20℃ or less, 10℃ or less, 5℃ or less, 0℃ or less, -5℃ or less, or -10℃ or less.

[0019] The first monomer may be, for example, a hydroxy group-containing monomer such as 2-hydroxyalkyl(meth)acrylate, a polymerizable heterocyclic monomer such as vinylpyrrolidone, a (meth)acrylamide-based monomer such as (meth)acrylamide, N-alkyl(meth)acrylamide, or N,N-dialkyl(meth)acrylamide, an acidic monomer such as (meth)acrylic acid, maleic acid, or itaconic acid, glyceryl(meth)acrylate, or a monomer containing an alkylene oxide unit, etc. Among the above monomers, an acidic monomer may be suitable as the first monomer.

[0020] As used herein, the term (meth)acrylic means acrylic or methacrylic.

[0021] In this specification, unless otherwise specified, the term alkyl or alkyl group refers to a straight-chain, branched-chain or cyclic alkyl or alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms. The alkyl or alkyl group may be optionally substituted with one or more substituents or may be an unsubstituted alkyl or alkyl group.

[0022] The monomer containing an alkylene oxide unit may be, for example, a monomer represented by the following formula 1 or 2.

[0023] [ka]

[0024] In Chemical Formula 1, Q is hydrogen or an alkyl group, U is an alkylene group, Z is hydrogen or an alkyl group, and m is an arbitrary number.

[0025] [ka]

[0026] In Chemical Formula 2, Q is hydrogen or an alkyl group, A and U are each independently an alkylene group, X is hydrogen, an alkyl group, a hydroxyl group or a cyano group, and n is an arbitrary number.

[0027] In Chemical Formulas 1 and 2, the alkylene group may be exemplified by an alkylene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkylene group may be linear, branched, or cyclic. The alkylene group may be optionally substituted with one or more substituents.

[0028] In Chemical formulas 1 and 2, the alkyl group present in Q and Z may be exemplified by an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may be optionally substituted with one or more substituents.

[0029] In Chemical Formulas 1 and 2, m and n are any numbers, and may be, for example, each independently a number within the range of 1 to 100, 1 to 90, 1 to 80, 1 to 70, 1 to 60, 1 to 50, 1 to 40, 1 to 30, 1 to 20, 1 to 16, or 1 to 12.

[0030] In one example, the first monomer may be a compound represented by Chemical Formula 1, in which Q is hydrogen or an alkyl group having 1 to 4 carbon atoms, U is an alkylene group having 1 to 4 carbon atoms, Z is hydrogen or an alkyl group having 1 to 4 carbon atoms, and m is about 1 to 30, but is not limited thereto.

[0031] In the polymer, the ratio of the polymerized units of the first monomer as described above may be controlled in consideration of the desired physical properties, such as oil resistance.

[0032] For example, the ratio of the polymerization units of the first monomer to the total polymerization units contained in the polymer may be about 1 to 40% by weight. In other examples, the ratio may be about 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 3% by weight or more, 3.5% by weight or more, 4.5% by weight or more, 5% by weight or more, 5.5% by weight or more, 6% by weight or more, 6.5% by weight or more, 7% by weight or more, 7.5% by weight or more, 8% by weight or more, 8.5% by weight or more, 9% by weight or more, 9.5% by weight or more, 10% by weight or more, 11% by weight or more, 12% by weight or more, 13% by weight or more, 14% by weight or more, or 14.5% by weight or more, and may be about 39% by weight or less, 38% by weight or less, 37% by weight or less, 36% by weight or less, 35% by weight or less, 37 ... It may be about 4% by weight or less, 33% by weight or less, 32% by weight or less, 31% by weight or less, 30% by weight or less, 29% by weight or less, 28% by weight or less, 27% by weight or less, 26% by weight or less, 25% by weight or less, 24% by weight or less, 23% by weight or less, 22% by weight or less, 21% by weight or less, 20% by weight or less, 19% by weight or less, 18% by weight or less, 17% by weight or less, 16% by weight or less, 15% by weight or less, 14% by weight or less, 13% by weight or less, 12% by weight or less, 11% by weight or less, 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, or 5.5% by weight or less. Under such a ratio, a polymer composition having a desired physical property can be provided. For example, the higher the ratio of the polymerization unit of the first monomer, the more advantageous it may be in terms of the above-mentioned oil resistance. However, since the first monomer is a relatively hydrophilic monomer, it is not easy to include the first monomer in a polymer at an appropriate level, for example, by exhibiting a thickening effect during emulsion polymerization in an aqueous solvent. However, for example, by using a so-called seed emulsion polymerization method, a polymer composition including a polymer having a relatively high ratio of the first monomer can be efficiently produced.

[0033] Thus, in one example, the polymer may be a seed emulsion polymer. The seed emulsion polymer refers to a polymer formed by seed emulsion polymerization. Such seed emulsion polymerization may be carried out by the method described in the present specification below.

[0034] The second monomer is a monomer having a relatively hydrophobic property with respect to the first monomer. In another example, the solubility parameter of the second monomer is 10.5 (cal / cm 3 ) 1 / 2 Below, 10(cal / cm 3 ) 1 / 2 Below, 9.5(cal / cm 3 ) 1 / 2 Less than or equal to 9 (cal / cm 3 ) 1 / 2 It may be less than 4 (cal / cm 3 ) 1 / 2 Above, 5(cal / cm 3 ) 1 / 2 Above, 6(cal / cm 3 ) 1 / 2 Above, 7(cal / cm 3 ) 1 / 2 Above, 8(cal / cm 3 ) 1 / 2 Above, 8.5(cal / cm 3 ) 1 / 2 Above, 9(cal / cm 3 ) 1 / 2 Above, 9.5(cal / cm 3 ) 1 / 2 or above 10(cal / cm 3 ) 1 / 2 It may be more than that.

[0035] The second monomer may be a monomer appropriately selected from monomers known to have the above-mentioned solubility parameters. The second monomer is included in the polymer together with the first monomer to ensure oil resistance and contribute to the formation of a film-forming agent, cosmetic, or pharmaceutical product that is free of powdering or bleeding.

[0036] Examples of monomers that can be used as the second monomer include alkyl (meth)acrylates or aromatic (meth)acrylates. In this application, the term (meth)acrylate means acrylate or methacrylate.

[0037] Examples of the alkyl group contained in the alkyl (meth)acrylate include linear, branched, or cyclic alkyl groups having 2 to 20, 2 to 16, 2 to 12, or 2 to 8 carbon atoms, and the alkyl group may be optionally substituted with one or more substituents. Examples of such monomers include, but are not limited to, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate, isobornyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, or lauryl (meth)acrylate.

[0038] Examples of the aromatic (meth)acrylate include aryl (meth)acrylate and aryl alkyl (meth)acrylate. The aryl group of the aryl or aryl alkyl may be, for example, an aryl group having 6 to 24 carbon atoms, 6 to 18 carbon atoms, or 6 to 12 carbon atoms. The alkyl group of the aryl alkyl may be, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic, and the alkyl group or aryl group may be optionally substituted with one or more substituents.

[0039] The aryl group or arylalkyl group may be exemplified by a phenyl group, a phenylethyl group, a phenylpropyl group, a naphthyl group, and the like, but is not limited thereto.

[0040] As the second monomer, for example, a monomer represented by the following formula 3 may be used.

[0041] [ka]

[0042] In Chemical formula 3, Q is hydrogen or an alkyl group, and B may be a linear or branched alkyl group or an alicyclic hydrocarbon group having two or more carbon atoms, or may be an aromatic substituent such as an aryl group or an arylalkyl group.

[0043] In Chemical formula 3, the alkyl group present in Q may be exemplified by an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may be optionally substituted with one or more substituents.

[0044] In Chemical formula 3, B may be a straight-chain or branched-chain alkyl group having 2 or more carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, or 2 to 10 carbon atoms.

[0045] In another example, in Chemical formula 3, B may be an alicyclic hydrocarbon group, for example, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms, and examples of such a hydrocarbon group may include an alicyclic alkyl group having 3 to 20 carbon atoms, 3 to 16 carbon atoms, or 6 to 12 carbon atoms, such as a cyclohexyl group or an isobornyl group. Compounds having such an alicyclic hydrocarbon group are also known as relatively hydrophobic compounds.

[0046] In order to ensure the desired physical properties, the second monomer may be a mixture of at least two types of monomers.

[0047] For example, the second monomer may be a monomer (A) having a relatively high glass transition temperature (hereinafter, Tg) and a monomer (B) having a relatively low Tg. Thus, for example, the polymer may include, as the polymerization units of the second monomer, a polymerization unit of the monomer (A) having a Tg of 20° C. or more and a polymerization unit of the monomer (B) having a Tg of less than 20° C.

[0048] The Tg of a monomer referred to herein is the Tg known for the homopolymer made of that monomer.

[0049] In other examples, the Tg of the monomer (A) may be 25°C or higher, 30°C or higher, 35°C or higher, 40°C or higher, 45°C or higher, 50°C or higher, 55°C or higher, 60°C or higher, 65°C or higher, 70°C or higher, 75°C or higher, 80°C or higher, 85°C or higher, 90°C or higher, 95°C or higher, or 100°C or higher, and may be about 150°C or lower, 145°C or lower, 140°C or lower, 135°C or lower, 130°C or lower, 125°C or lower, 120°C or lower, 115°C or lower, 110°C or lower, 105°C or lower, 100°C or lower, 95°C or lower, 90°C or lower, 85°C or lower, 80°C or lower, 75°C or lower, or 70°C or lower. In addition, in other examples, the Tg of the monomer (B) may be 15°C or less, 10°C or less, 5°C or less, 0°C or less, -5°C or less, -10°C or less, -15°C or less, -20°C or less, -25°C or less, -30°C or less, -35°C or less, -40°C or less, or -45°C or less, but may also be -150°C or more, -145°C or more, -140°C or more, -135°C or more, -130°C or more, -125°C or more, -120°C or more, -115°C or more, -110°C or more, -105°C or more, -100°C or more, -95°C or more, -90°C or more, -85°C or more, -80°C or more, -75°C or more, -70°C or more, -65°C or more, -60°C or more, or -55°C or more.

[0050] When a mixture of two monomers is used as the second monomer, as described above, the Tg of the entire polymer can be maintained at an appropriate level, which is advantageous in forming a polymer having oil resistance as well as other desired physical properties (e.g., prevention of bleeding and powdering).

[0051] As the monomer (A) and the monomer (B), appropriate types may be selected from the above-mentioned monomers mentioned as the second monomer, taking into consideration the Tg of the monomer.

[0052] For example, as the monomer (A), a compound may be used in which Q in the above formula 3 is an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or a methyl group, and B is a straight-chain or branched-chain alkyl group having 2 or more carbon atoms. In such a case, the alkyl group of B may be a straight-chain or branched-chain alkyl group having 2 to 4 carbon atoms.

[0053] For example, the monomer (B) may be a compound represented by Chemical formula 3, in which Q is hydrogen and B is a straight-chain or branched-chain alkyl group having 2 or more carbon atoms, 4 or more carbon atoms, or 6 or more carbon atoms. In such a case, the upper limit of the carbon number of the alkyl group of B is not particularly limited and may be, for example, about 20, 18, 16, 14, 12, or 10.

[0054] In the polymer, the ratio of the polymerization units of the second monomer may be within the range of 150 to 4000 parts by weight relative to 100 parts by weight of the polymerization units of the first monomer. In other examples, the ratio is about 200 parts by weight or more, 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, 550 parts by weight or more, 600 parts by weight or more, 650 parts by weight or more, 700 parts by weight or more, 750 parts by weight or more, 800 parts by weight or more, 850 parts by weight or more, 900 parts by weight or more, 950 parts by weight or more, 1000 parts by weight or more, 1100 parts by weight or more, 1200 parts by weight or more, 1300 parts by weight or more, 1400 parts by weight or more, 1500 parts by weight or more, 1600 parts by weight or more, 1700 parts by weight or more, 1800 parts by weight or more, or 1 It may be 850 parts by weight or more, and may be about 2350 parts by weight or less, 2300 parts by weight or less, 2250 parts by weight or less, 2200 parts by weight or less, 2150 parts by weight or less, 2100 parts by weight or less, 2050 parts by weight or less, 2000 parts by weight or less, 1950 parts by weight or less, 1900 parts by weight or less, 1800 parts by weight or less, 1700 parts by weight or less, 1600 parts by weight or less, 1500 parts by weight or less, 1400 parts by weight or less, 1300 parts by weight or less, 1200 parts by weight or less, 1100 parts by weight or less, 1000 parts by weight or less, 900 parts by weight or less, 800 parts by weight or less, 700 parts by weight or less, or 600 parts by weight or less.

[0055] When the monomer (A) and the monomer (B) are applied as the polymerization units of the second monomer, the weight ratio (A / B) of the polymerization units of the monomer (A) and the polymerization units of the monomer (B) may be within a range of 0.25 to 5. In other examples, the weight ratio (A / B) may be about 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, 0.8 or more, 0.85 or more, 0.9 or more, 0.95 or more, 1.0 or more, 1.5 or more, or 2 or more, and may be about 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, 2 or less, 1.5 or less, 1 or less, 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, or 0.7 or less.

[0056] The polymer may appropriately contain other known monomers in addition to the first and second monomers described above, as long as the desired physical properties are not impaired.

[0057] The Tg of the polymer of the present application may be, for example, within the range of about -30°C to 30°C. In other examples, the Tg of the polymer may be about -25°C or more, -20°C or more, -15°C or more, or -10°C or more, but may be about 25°C or less, 20°C or less, 15°C or less, 10°C or less, 5°C or less, 0°C or less, or -5°C or less. The Tg is a theoretical value calculated from the monomer composition of the polymer by the so-called Fox equation. The Tg may be useful, for example, when the polymer is applied as a film-forming agent for cosmetics, pharmaceuticals, etc. By using the polymer within the Tg range, it is possible to efficiently form a film having excellent oil resistance without stickiness, bleeding, or crushing.

[0058] In the present application, the polymer may have a weight average molecular weight (Mw) in the range of 100,000 to 2,000,000. In the present application, the weight average molecular weight is, for example, a converted value relative to standard polystyrene measured using GPC (Gel Permeation Chromatograph), and unless otherwise specified, the term molecular weight may refer to the weight average molecular weight. The molecular weight (Mw) as described above may be useful, for example, when the polymer is applied as a film forming agent. By using the polymer in the above molecular weight (Mw) range, it is possible to efficiently form a film having excellent oil resistance without stickiness, bleeding, crushing, etc.

[0059] In other examples, the molecular weight (Mw) may be 150,000 or more, 200,000 or more, 250,000 or more, 300,000 or more, 350,000 or more, 400,000 or more, 450,000 or more, or 500,000 or more, and may be about 1.9 million or less, 1.8 million or less, 1.7 million or less, 1.6 million or less, 1.5 million or less, 1.4 million or less, 1.3 million or less, 1.2 million or less, 1.1 million or less, 1 million or less, 900,000 or less, 800,000 or less, or 700,000 or less.

[0060] The polymer composition of the present application including the polymer may not contain methanol or may contain a minimum amount of methanol. For example, the content of methanol in the polymer composition may be about 30 ppm or less, 25 ppm or less, 20 ppm or less, 15 ppm or less, 10 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, 1 ppm or less, or 0.5 ppm or less. That is, polymers known for producing film formers, etc., have the type and ratio of monomers controlled to adjust Tg, etc., and some of the monomers known as such monomers generate methanol by hydrolysis, etc. For example, methyl (meth)acrylate is very often used to adjust Tg in the production of polymers that form film formers, but it generates methanol by hydrolysis, etc. The generated methanol generates formaldehyde, which is a typical harmful substance in polymer compositions, film formers, cosmetics, and pharmaceuticals. However, in the present application, a polymer composition, film former, cosmetic, or pharmaceutical product that does not contain methanol or contains a minimum amount of methanol may be provided by not using or minimizing the ratio of a monomer that produces methanol among monomers that form a polymer. However, since the monomer that produces methanol is known to be very effective in controlling physical properties such as Tg of a polymer, it is not easy to achieve the desired physical properties without using such a monomer. However, in the present application, a polymer composition that does not contain methanol or contains a small amount of methanol but has the desired physical properties may be provided by using the above-mentioned first and second monomers, monomer (A) and monomer (B). Since it is most appropriate that no methanol is contained in the polymer composition, the lower limit of the ratio of methanol may be about 0 ppm.

[0061] The polymer composition of the present application does not contain methanol or contains a minimum amount of methanol, and therefore does not contain or contains a minimum amount of formaldehyde, which is a harmful substance generated thereby. For example, the formaldehyde content of the polymer composition may be about 30 ppm or less, 25 ppm or less, 20 ppm or less, 15 ppm or less, 10 ppm or less, 5 ppm or less, 4 ppm or less, 3 ppm or less, 2 ppm or less, 1 ppm or less, or 0.5 ppm or less. Since it is most appropriate that no formaldehyde is contained in the polymer composition, the lower limit of the formaldehyde ratio may be about 0 ppm.

[0062] The ratios of methanol and formaldehyde as described above are measured by the method described in the Examples below.

[0063] To form a polymer composition having the above-mentioned ratio of methanol and formaldehyde, the polymer does not need to contain a polymerization unit of a methanol-producing monomer. Examples of monomers that produce methanol upon hydrolysis or the like and are widely used in the manufacture of film-forming agents include methyl methacrylate and methacrylate.

[0064] As a monomer having a relatively hydrophobic property (e.g., the second monomer in the present application) or a monomer having a relatively high Tg (e.g., the monomer (A) in the present application) that is applied to a polymer forming a film former, a monomer having a methyl group such as methyl methacrylate is often used. However, in the present application, the type of monomer mentioned as the second monomer does not produce methanol or, if produced, produces only a very small amount of methanol. Therefore, in the present application, it is appropriate to apply only the type of monomer mentioned above as the second monomer, particularly as the monomer (A) among at least the second monomers.

[0065] Therefore, in one example, the polymer may contain only polymerization units of the monomer represented by Chemical Formula 3 as polymerization units of the second monomer or monomer (A).

[0066] For example, the polymer may be applied with only polymerization units of a compound in which, as at least the polymerization unit of the monomer (A), in Chemical Formula 3, Q is an alkyl group, for example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or a methyl group, and B is a straight-chain or branched-chain alkyl group having 2 or more carbon atoms, and in such a case, the alkyl group of B may be a straight-chain or branched-chain alkyl group having 2 to 4 carbon atoms.

[0067] The polymer composition of the present application may comprise only the polymer, or may comprise the polymer plus other necessary components.

[0068] Such a necessary component may be, for example, a formaldehyde remover. Applicable formaldehyde removers may be, for example, ammonia, urea, sodium bisulfite, and / or sodium metabisulfite, but are not limited thereto. The proportion of the formaldehyde remover in the polymer composition is at an appropriate level, and may be, for example, about 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, 6 parts by weight or less, 5 parts by weight or less, 4 parts by weight or less, or 3 parts by weight or less, relative to 100 parts by weight of the polymer. The formaldehyde remover may be about 0 parts by weight or more, more than about 0 parts by weight, 0.5 parts by weight or more, 1 part by weight or more, 1.5 parts by weight or more, or 2.5 parts by weight or more, relative to 100 parts by weight of the polymer.

[0069] The polymeric composition may suitably further comprise additives further required for said polymer and / or formaldehyde scavenging agent.

[0070] Examples of such additives include, but are not limited to, oils, surfactants, purified water, polyhydric alcohols (e.g., glycerin, propylene glycol, butylene glycol, etc.), organic powders, inorganic powders, UV absorbers, preservatives, antifoaming agents, antibacterial agents, antioxidants, cosmetic ingredients, fragrances, thickeners, gelling agents, metal soaps, water-soluble polymers, fat-soluble polymers, fibers (nylon, rayon, etc.), pigments and / or pearling agents.

[0071] The polymer composition may be prepared by various known methods. In consideration of the efficiency of polymer formation and application, it is effective to apply an emulsion polymerization method. For example, an emulsion polymerization method using an aqueous solvent such as water as a continuous phase may be applied.

[0072] In particular, when it is desired to form a polymer containing the first monomer and having a high ratio of polymerized units of the first monomer, it is effective to apply the seed emulsion polymerization method among the emulsion polymerization methods. Seed emulsion polymerization is a polymerization method in which a homogeneous or heterogeneous monomer is polymerized in a seed, which is a relatively small particle of an emulsion polymer that has been polymerized in advance, to grow the particle. When this method is applied, the polymer targeted in the present application can be more effectively produced.

[0073] The seeded emulsion polymerization process may include, for example, a seed polymerization stage and a seed growth stage.

[0074] In one example, the polymerization method may include a first step of performing seed emulsion polymerization of a reaction solution containing a monomer mixture, an aqueous solvent, and a surfactant, and a second step of performing emulsion polymerization while adding a reaction solution containing a monomer mixture to the seed emulsion polymer of the first step, thereby growing the seeds generated in the first step.

[0075] The monomer mixture applied in the first and second steps may include the first and second monomers described above, and the second monomer may include the monomer (A) and monomer (B) described above. In this case, the ratio of each monomer in the monomer mixture may be adjusted so that the polymerized units are formed in the above ratio, and in one example, may be approximately similar to the ratio of the polymerized units described above.

[0076] For example, the first monomer in the monomer mixture may be about 1 to 40% by weight. In other examples, the ratio may be about 1.5% by weight or more, 2% by weight or more, 2.5% by weight or more, 3% by weight or more, 3.5% by weight or more, 4.5% by weight or more, 5% by weight or more, 5.5% by weight or more, 6% by weight or more, 6.5% by weight or more, 7% by weight or more, 7.5% by weight or more, 8% by weight or more, 8.5% by weight or more, 9% by weight or more, 9.5% by weight or more, 10% by weight or more, 11% by weight or more, 12% by weight or more, 13% by weight or more, 14% by weight or more, or 14.5% by weight or more, and may be about 39% by weight or less, 38% by weight or less, 37% by weight or less, 36% by weight or less, 35% by weight or less, 37% by weight or less, 38 ... It may be about 4 weight% or less, 33 weight% or less, 32 weight% or less, 31 weight% or less, 30 weight% or less, 29 weight% or less, 28 weight% or less, 27 weight% or less, 26 weight% or less, 25 weight% or less, 24 weight% or less, 23 weight% or less, 22 weight% or less, 21 weight% or less, 20 weight% or less, 19 weight% or less, 18 weight% or less, 17 weight% or less, 16 weight% or less, 15 weight% or less, 14 weight% or less, 13 weight% or less, 12 weight% or less, 11 weight% or less, 10 weight% or less, 9 weight% or less, 8 weight% or less, 7 weight% or less, 6 weight% or less, or 5.5 weight% or less.

[0077] The second monomer in the monomer mixture may be contained in a range of 150 to 4000 parts by weight relative to 100 parts by weight of the first monomer. In other examples, the ratio is about 200 parts by weight or more, 250 parts by weight or more, 300 parts by weight or more, 350 parts by weight or more, 400 parts by weight or more, 450 parts by weight or more, 500 parts by weight or more, 550 parts by weight or more, 600 parts by weight or more, 650 parts by weight or more, 700 parts by weight or more, 750 parts by weight or more, 800 parts by weight or more, 850 parts by weight or more, 900 parts by weight or more, 950 parts by weight or more, 1000 parts by weight or more, 1100 parts by weight or more, 1200 parts by weight or more, 1300 parts by weight or more, 1400 parts by weight or more, 1500 parts by weight or more, 1600 parts by weight or more, 1700 parts by weight or more, 1800 parts by weight or more, or 1 It may be 850 parts by weight or more, and may be about 2350 parts by weight or less, 2300 parts by weight or less, 2250 parts by weight or less, 2200 parts by weight or less, 2150 parts by weight or less, 2100 parts by weight or less, 2050 parts by weight or less, 2000 parts by weight or less, 1950 parts by weight or less, 1900 parts by weight or less, 1800 parts by weight or less, 1700 parts by weight or less, 1600 parts by weight or less, 1500 parts by weight or less, 1400 parts by weight or less, 1300 parts by weight or less, 1200 parts by weight or less, 1100 parts by weight or less, 1000 parts by weight or less, 900 parts by weight or less, 800 parts by weight or less, 700 parts by weight or less, or 600 parts by weight or less.

[0078] In addition, when the monomer (A) and the monomer (B) are applied to the monomer mixture as the second monomer, the weight ratio (A / B) of the monomer (A) and the monomer (B) may be within a range of 0.25 to 5. In other examples, the weight ratio (A / B) may be about 0.3 or more, 0.35 or more, 0.4 or more, 0.45 or more, 0.5 or more, 0.55 or more, 0.6 or more, 0.65 or more, 0.7 or more, 0.75 or more, 0.8 or more, 0.85 or more, 0.9 or more, 0.95 or more, 1.0 or more, 1.5 or more, or 2 or more, and may be about 4.5 or less, 4 or less, 3.5 or less, 3 or less, 2.5 or less, 2 or less, 1.5 or less, 1 or less, 0.95 or less, 0.9 or less, 0.85 or less, 0.8 or less, 0.75 or less, or 0.7 or less.

[0079] The ratio of the first and second monomers and the monomer (A) and the monomer (B) in the monomer mixture mentioned above may be a ratio determined based on the total of all monomer mixtures applied in the first and second stages. That is, as described below, in the polymerization method of the present application, first, components such as monomers and surfactants are dispersed in a solvent (aqueous solvent such as water) to prepare a reaction liquid, and then a part of the reaction liquid is divided and used for the seed emulsion polymerization in the first stage, and then the remaining part is introduced as a reaction liquid in the second stage, and therefore the ratio of the monomers may be based on the total of the monomer mixtures applied in the first and second monomers.

[0080] For the emulsion polymerization, a surfactant is applied together with the monomer mixture. As the surfactant, a known surfactant used in emulsion polymerization may be used. As such a surfactant, an anionic or nonionic surfactant may be exemplified, specifically, an anionic surfactant such as sodium lauryl sulfate (SLS), sodium dodecyl benzene sulfate (SDBS), ammonium lauryl sulfate (ALS), sodium cetyl stearyl sulfate, or sodium lauryl ether sulfate (SLES), or a nonionic surfactant known as Triton or Tween may be exemplified, and one or a mixture of two or more of the above may be applied.

[0081] The proportion of the surfactant may be appropriately adjusted depending on the purpose, and for example, the surfactant may be contained in the reaction liquid in an amount of about 0.5 to 20 parts by weight relative to 100 parts by weight of the monomer mixture. In other examples, the proportion may be about 1 part by weight or more, 1.5 parts by weight or more, 2 parts by weight or more, 2.5 parts by weight or more, 3 parts by weight or more, 3.5 parts by weight or more, or 4 parts by weight or more, and may be about 18 parts by weight or less, 16 parts by weight or less, 14 parts by weight or less, 12 parts by weight or less, 10 parts by weight or less, 9 parts by weight or less, 8 parts by weight or less, 7 parts by weight or less, or 6 parts by weight or less.

[0082] The proportion of the surfactant may be the proportion in the reaction liquid in the first stage, or, if a surfactant is also present in the second stage, it may be the proportion based on the sum of the reaction liquids in the first and second stages, as in the case of the monomer mixture.

[0083] The reaction liquid may be produced by dispersing the monomer mixture and / or the surfactant in a solvent (e.g., an aqueous solvent such as water). Therefore, the reaction liquid may further contain the solvent. The ratio of the solvent is not particularly limited, and in one example, the concentration of the monomer mixture in the solvent may be controlled to be within the range of about 5 to 90% by weight.

[0084] The method of initiating polymerization in the reaction solution to carry out the first stage is not particularly limited. For example, the first stage may be carried out by adding a known polymerization initiator to the reaction solution and controlling the conditions so that a polymerization reaction by the initiator is carried out.

[0085] As such an initiator, a known initiator, for example, a known water-soluble initiator may be used, and examples of the initiator include potassium peroxodisulfate (KPS), ammonium persulfate (APS), sodium persulfate, and / or hydrogen peroxide, but are not limited thereto.

[0086] The ratio of the initiator is not particularly limited, and an appropriate ratio may be applied depending on the purpose. The method of initiating polymerization by the initiator is also not particularly limited, and for example, if the initiator is a thermal initiator, a method of applying appropriate heat may be applied, and if the initiator is a photoinitiator, a method of irradiating appropriate light may be applied.

[0087] As described above, in the method, the monomer mixture and surfactant may be dispersed in a solvent to prepare a reaction liquid, a part of which may be subjected to the seed polymerization reaction of the first stage, and then the remaining part may be added to the seed polymer of the first stage to perform the second stage. In such a case, the method may include a step of dispersing the monomer mixture and surfactant in a solvent prior to the first stage to prepare a total reaction liquid, and then separating a part of the total reaction liquid to prepare the reaction liquid of the first stage. The proportion of the reaction liquid separated and applied to the first stage is not particularly limited, and for example, about 1 to 10% by weight of the total reaction liquid may be applied as the reaction liquid of the first stage.

[0088] In the method of the present application, the reaction solution added in the second step may further contain an aqueous solvent and a surfactant in addition to the monomer mixture. For example, when the entire reaction solution mentioned above is divided to perform the first step and the remaining reaction solution is applied to the second step, the reaction solution in the second step may also contain a surfactant, etc., as in the case of the reaction solution in the first step, and when the above method is not applied and a separate reaction solution is added in the second step, the reaction solution in the second step may also contain the surfactant, etc.

[0089] The rate at which the reaction solution is introduced in the second step may be controlled. By controlling the rate at which the reaction solution is introduced, a polymer having the desired monomer composition and properties can be more effectively formed.

[0090] For example, the rate at which the reaction solution is added in the second step may be adjusted to be slower than the reaction rate of the monomer.

[0091] The method of initiating polymerization while adding the reaction solution to carry out the second stage as described above is not particularly limited, and for example, the second stage may be carried out by adding a known polymerization initiator together with the reaction solution as in the first stage, and controlling the conditions so that a polymerization reaction is carried out by the initiator. In this case, the type and ratio of the initiator that may be applied, and the method of initiating polymerization by the initiator are the same as in the first stage.

[0092] The method for preparing a polymer composition of the present application may further include a step of mixing the polymer formed after the first and second steps with other necessary ingredients, such as a formaldehyde remover.

[0093] The present application further relates to a film-forming agent, cosmetic composition, or cosmetic comprising the polymer. The polymer can be used to provide a film-forming agent that can form a uniform film by application, exhibits high stability when applied to the skin, and has excellent oil resistance, anti-bleeding, and anti-powdering properties, and minimizes the proportion of harmful ingredients.

[0094] Thus, the polymer may be applied to the manufacture of a film-forming agent or a cosmetic composition that may be used in the manufacture of various cosmetics including beauty packs, makeup such as mascara applied to the mouth or eyes, nail polish applied to fingernails or toenails, lipstick, eye shadow, hair styling products, eyeliner, etc. Furthermore, the polymer or film-forming agent may be applied to medical uses due to the above-mentioned properties, and examples of medical uses include bandages and transdermal absorption preparations.

[0095] In the film-forming agent, cosmetic composition, or cosmetic, the proportion of the polymer is not particularly limited and may be selected in consideration of the application, etc. For example, when the polymer is applied to a cosmetic composition, the concentration of the polymer in the composition may be within the range of 1% by weight to 20% by weight, but is not limited thereto.

[0096] The film-forming agent, cosmetic composition or cosmetic may further contain other active ingredients depending on the application. Examples of the additional active ingredients include cosmetic ingredients such as whitening and UV protection, as well as medicinal ingredients, physiologically active ingredients or pharmacologically active ingredients. Examples of such active ingredients include local anesthetic ingredients (lidocaine, dibucaine hydrochloride, dibucaine, ethyl aminobenzoate, etc.), analgesic ingredients (salicylic acid derivatives such as methyl salicylate, indomethacin, piroxicam, ketoprofen, felbinac, etc.), anti-inflammatory ingredients (glycyrrhizic acid, glycyrrhetinic acid salts such as dipotassium glycyrrhetinate, glycyrrhetinic acid, stearyl glycyrrhetinate, bufexamac, benzyl nicotinate, hydrocortisone, hydrocortisone butyrate, hydroxypropyl acetone ... Cortisone, frednisone acetate valerate, frednisolone acetate, frednisone, dexamethasone, dexamethasone acetate, dimethylisopropylazulene ibuprofen piconol, arnica extract, scutellaria extract, cattail extract, chamomile extract, calamine, licorice extract, guaiazulene, gardenia extract, gentiana extract, black tea extract, tocopherol, tocopherol acetate, purple root extract, perilla extract, peony extract, sage extract, swertia jasmine extract, mulberry bark extract, piconol hydrochloride Lidoxine, peach leaf extract, cornflower extract, saxifrage extract, mugwort extract, Roman chamomile extract, etc.), antihistamine ingredients (chlorpheniramine maleate, diphenhydramine, diphenhydramine hydrochloride, diphenhydramine salicylate, isobenzylic hydrochloride, etc.), local irritant ingredients (ammonia, l-menthol dl-camphor, peppermint oil, benzyl nicotinate, vanillylamide nonyl acid, etc.), antipruritic ingredients (crotamiton, etc.), preservative or bactericidal ingredients (acrinol, glutamic acid, etc.), Chlorhexidine conate, chlorhexidine hydrochloride, benzalkonium chloride, benzethonium chloride, povidone iodine, iodine form, iodine, potassium iodide, merbromin, hydrogen peroxide, cresol, triclosan, phenol, isopropyl methylphenol, thymol, sodium salicylate, undecylenic acid, photosensitizer, hinokitiol, phenoxyethanol, chlorobutanol, quaternium 73, zinc pyrithione, paraoxybenzoic acid esters, eucalyptus extract,Resorcinol rosemary extract, etc.), antifungal ingredients (imidazole antifungal agents such as clotrimazole, clotrimazole acetate, miconazole acetate, econazole acetate, bifonazole, oxiconazole acetate, sulconazole acetate, neticonazole hydrochloride, bifonazole and tioconazole, omoconazole acetate, etc., allylamine antifungal agents such as terbinafine, terbinafine hydrochloride and naftifine, benzylamine antifungal agents such as butenafine, allylamine antifungal agents such as amorolfine hydrochloride, tolnaftate, tolciclate, etc. Ocarbamic acid antifungals, pyrrolnitrin, exalamide, ciclopirox olamine, etc.), tissue repair ingredients (allantoin, heparinoids, vitamin A palmitate, vitamin D2, retinol acetate, retinol, vitamin A oil, panthenol, etc.), astringent ingredients (zinc oxide, gasiogapi extract, aluminum chloride, fanbak extract, its salt, citric acid, white birch extract, body extract, hop extract, horse chestnut extract, etc.), keratin softening ingredients (urea, glycerin, non-glycerin, potassium hydroxide, salicylic acid, sulfur, colloidal sulfur, resorcin, glycerin, etc.), alcoholic acid, lactic acid, sodium sulfate, etc.), moisturizing ingredients (butylene glycol, sodium pyrrolidone carboxylate, propylene glycol, sodium ribonucleic acid, Myoichiba extract, asuraginsan, alanine, arginine sodium alginate, Althea extract, aloe vera extract, oyster extract, hydrolyzed keratin, hydrolyzed collagen, hydrolyzed annyongkirion, hydrolyzed eggshell membrane, hydrolyzed egg white, hydrolyzed silk, brown algae extract, quince extract, raspberry extract, xylitol, chitosan, cucumber extract, quince seed extract, glycine, glycerin , glucose, Cape aloe extract, cystin, cysteine, mallow extract, serine, sorbitol, trehalose, sodium lactate, sodium hyaluronate, placenta extract, loofah extract, multi-use agent, mannitol, lily extract, lactoferrin, lysine, apple extract, royal jelly extract, etc.) emollient ingredients (almond oil, avocado oil, olive oil, oleic acid, orange roughy oil, cocoa butter, carrot extract, squalane, ceramide, evening primrose oil, grape seed oil, jojoba oil, macadamia nut oil, mineral oil, mink oil,Eucalyptus oil, rosehip oil, varelin, etc.), whitening ingredients (ascorbic acid, ascorbic acid derivatives, arbutin, lesinol, ellagic acid, glutathione, kojic acid, aged cane extract, kiwi extract, etc.), UV protection ingredients (para-aminobenzoic acid, ethyl ester of para-aminobenzoic acid, glycerin ester of para-aminobenzoic acid, amyl alcohol ester of para-dimethylaminobenzoic acid, 2-ethylhexyl alcohol ester of para-dimethylaminobenzoic acid, t-butyl methoxydibenzoylmethane, o Examples of the active ingredient include, but are not limited to, xybenzones, octyl triazone, octyl salicylate, ethyl diisopropylcinnamate, methyl diisopropylcinnamate, cinoxate, glyceryl dimethoxycinnamate octanoate, dimethoxybenzylidene dioxoimidazolidine octyl propionate, chape extract, drometrizole, isopropyl paramethoxycinnamate, homosalate, octyl methoxycinnamate, etc.), herbal extract ingredients, vitamins, amino acids, and minerals.

[0097] The film-forming agent, cosmetic composition or cosmetic product may contain other solvents, solvents or additives depending on the application.

[0098] Examples of the solvent or solvent component may include, depending on the application and form of use of the composition, for example, alcohol (e.g., polyethylene glycol, etc.), ether (diethyl ether, etc., glycol ethers (cellosolve types such as methyl cellosolve, dialkylene glycol alkyl ethers such as diethylene glycol monoethyl ether, etc.), nitrile (acetonitrile, etc.), ketone (acetone, etc.), or ester (carboxylic acid alkyl ester such as ethyl acetate, etc.).

[0099] Examples of additives include, of course, plasticizers, wetting agents, defoamers, colorants, preservatives, fragrances, flavorings, pigments, or thickeners, as well as conventional components used in quasi-drugs, pharmaceuticals, or cosmetics, such as powdered bases or carriers (binders, disintegrants, excipients, or lubricants), oily bases or carriers (animal and vegetable oils, waxes, petrolatum, paraffin oil, silicone oil, higher fatty acid esters, or higher fatty acids), aqueous bases or carriers (gel bases such as xanthan gum), preservatives, chelating agents, antioxidants, refreshing agents, stabilizers, fluidizing agents, emulsifiers, thickening agents, buffers, dispersants, adsorbents, moisturizers, wetting agents, moisture-proofing agents, antistatic agents, or other resins (olefin-based resins such as polyamide-based resins and hydrogenated polybutene), but are not limited thereto.

[0100] The method of producing the film-forming agent, cosmetic composition, or cosmetic product using the above-mentioned components or additional known components as necessary is not particularly limited, and known methods may be applied. Effect of the Invention

[0101] The present application aims to provide a polymer composition capable of forming cosmetics that have excellent oil resistance and do not bleed or fall off during use, and a film former or cosmetics produced using the same.

[0102] The present application aims to provide a polymer composition capable of forming cosmetics that have excellent oil resistance and do not bleed or fall off during use, and a film former or cosmetics produced using the same. [Brief description of the drawings]

[0103] [Figure 1] FIG. 1 is a photograph of the polymer prepared in Example 3. [Diagram 2] FIG. 2 is a photograph of the polymer prepared in Example 4. [Diagram 3]FIG. 3 is a photograph of the polymer produced in Reference Example 4. [Figure 4] FIG. 4 is a photograph of the polymer produced in Reference Example 5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0104] Hereinafter, the polymers of the present application will be described in detail with reference to examples and comparative examples, but the scope of the polymers is not limited to the following examples. In the following examples and comparative examples, each physical property was evaluated by the following method.

[0105] 1. Measurement of methanol and formaldehyde ratio The ratio of methanol was confirmed by GC-FID (Gas Chromatography Flame Ionization Detector). The measurement equipment used was Agilent Technologies' 7890B GC System, and the sample was diluted with ACN (acetonitrile) to confirm the ratio of methanol. The measurement conditions for confirming the ratio of methanol were as follows.

[0106] <Measurement conditions> Measuring instrument: 7890B GC System (Agilent Technologies) Column: HP-FFAP (19091F-115) (50m * 320μm * 0.5μm) Injector temperature: 220℃ Oven temperature:60℃ / 10min-25℃ / min-220℃ / 13min Flow rate: 1.5mL / min Injection volume: 1.5μL injection

[0107] The formaldehyde ratio was confirmed by LC-UV (Liquid Chromatography-UV). The measurement equipment used was an Agilent Technologies 1260 Infinity II LC product. The sample was expressed in water, and the formaldehyde ratio was confirmed after 1 hour of ultrasonic extraction. The measurement conditions for confirming the formaldehyde ratio are as follows:

[0108] <Measurement conditions> Column: C18 (5 μm, 4.6 * 250mm) Mobile phase: ACN:Water=60:40 Oven temperature: 30℃ Injection volume: 10μL Detection: 360 nm

[0109] 2. Molecular Weight Measurement The weight average molecular weight (Mw) and molecular weight distribution (PDI) were measured using GPC under the following conditions, and the measurement results were converted into a calibration curve using standard polystyrene from an Agilent system.

[0110] <Measurement conditions> Measuring instrument: Agilent GPC (Agilent 1200 series, US) Column: PL Mixed B 2 connected Column temperature: 40℃ Eluent: THF (Tetrahydrofuran) Flow rate: 1.0mL / min Concentration: ~1mg / mL (100μL injection)

[0111] 3. Calculation of glass transition temperature The glass transition temperature (Tg) was calculated based on the monomer composition using the following formula.

[0112] <Formula> 1 / Tg=ΣWn / Tn

[0113] In the above formula, Wn is the weight fraction of each monomer in the polymer, Tn is the glass transition temperature when the monomer forms a homopolymer, and the right side of the formula is the sum of all the calculated values ​​obtained by dividing the weight fraction of the monomer used by the glass transition temperature when the monomer forms a homopolymer (Wn / Tn) for each monomer.

[0114] 4. Evaluation of bleeding The evaluation of bleeding was carried out in the following manner. First, a sample (mascara type) was applied to a glass plate to a thickness of about 100 μm, and then dried at 25° C. for 24 hours. After that, about 4 cm of the dried sample was 2 After dropping 0.1g of artificial sebum onto the surface and wetting for 10 minutes, paper was placed on top of it and a 500g weight was used to perform horizontal back and forth motion 20 times. The extent to which the artificial sebum oozed onto the paper was analyzed by image analysis.

[0115] The artificial sebum used contained 40% by weight of triglyceride, 2.2% by weight of diglyceride, 16.4% by weight of free fatty acid, 12% by weight of squalane, 25% by weight of wax ester, 1.4% by weight of cholesterol, and 2% by weight of cholesterol ester.

[0116] Through image analysis, the color difference meter measurement value of the paper in the case where the sample was applied and dried, and then the artificial sebum was removed and the sample bled onto the paper was determined by dividing the color difference meter measurement value of the paper in which the sample was not applied but was removed onto the artificial sebum. The higher this value, the better the bleed prevention properties.

[0117] 5. Evaluation of powder fall Powder shedding was evaluated in the following manner. First, the mascara formulation was applied 10 times to a free strand of human hair, and after drying, the dried human hair sample was immersed in distilled water at 25°C for 5 seconds and then removed. The human hair was dried for 3 minutes, and then rubbed 20 times with a nylon brush at an amplitude of 2cm or less and the amount of powder that fell off was compared through image analysis. Powder shedding values ​​were calculated by applying the formulation to a human hair strand, drying it, immersing it in water, removing it, and rubbing it to measure the number of powder particles that fell off.

[0118] 6. Panel Evaluation A mascara use test was conducted by a 20-person expert evaluation panel (aged 25-50). After applying the mascara to the panel, they rated the degree of bleeding (the degree to which it bleeds into the sebum) and powdering after 6 hours on a 5-point scale according to the following criteria, and the average was used to judge the results.

[0119] <Evaluation criteria for bleeding and powder fall-off> A: Average of 4.5 points or more B: Average score 3.5 or more, less than 4.5 C: Average score 2.5 or more, less than 3.5 D: Average score below 2.5 points <Score evaluation criteria> <Evaluation of bleeding> 5 points: No bleeding 4 points: Slightly blurred 3 points: Average 2 points: Severe bleeding 1 point: Very severe bleeding <Evaluation of powder fall> 5 points: No powder falling off 4 points: Little powder fall 3 points: Average 2 points: A lot of powder falling off 1 point: Too much powder falling off

[0120] Example 1. 200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0121] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and acrylic acid (solubility parameter: 13.6 (cal / cm 3 ) 1 / 2 , Tg 105 °C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 110g, ethyl methacrylate (solubility parameter: 9.7 (cal / cm 3 ) 1 / 2 80g of dimethylformamide (Tg: 65°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added and polymerization was performed for 24 hours. In this process, the introduction rate of the emulsion was controlled to about 85mL / min. Through the above process, a polymer polymerization liquid with excellent phase stability without an increase in viscosity was obtained. The molecular weight (Mw) of the prepared polymerization liquid was about 500,000 to 650,000, and the Tg was about -8.6°C. Next, 5g of an aqueous ammonia solution (28% by weight), which is a formaldehyde remover, was mixed with the polymerization liquid to prepare a polymer composition. Next, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation. The numbers in Table 1 below are weight ratios.

[0122] Example 2. 200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0123] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and methacrylic acid (solubility parameter: 12.3 (cal / cm 3 ) 1 / 2 , Tg: 225°C) 10g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2, Tg: -50°C) 115g, ethyl methacrylate (solubility parameter: 9.7 (cal / cm 3 ) 1 / 2 75g of dimethylformamide (Tg: 65°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added and polymerization was performed for 24 hours. During this process, the introduction rate of the emulsion was controlled to about 85mL / min. Through the above process, a polymer polymerization liquid with excellent phase stability without an increase in viscosity was obtained. The molecular weight (Mw) of the prepared polymerization liquid was about 500,000 to 650,000, and the Tg was about -9.0°C. Next, 5g of an aqueous ammonia solution (28% by weight), which is a formaldehyde remover, was mixed with the polymerization liquid to prepare a polymer composition. Next, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation.

[0124] Example 3. 200 g of purified water and 2.5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0125] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal / cm 3 ) 1 / 2 , Tg: -15°C) 30g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 90g, ethyl methacrylate (solubility parameter: 9.7 (cal / cm 3 ) 1 / 280g of dimethylformamide (Tg: 65°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the introduction rate of the emulsion was controlled to about 85mL / min. FIG. 1 is a photograph of the polymer polymerization liquid obtained through the above process. Through the above process, a polymer polymerization liquid with excellent phase stability without an increase in viscosity was obtained. The molecular weight (Mw) of the prepared polymerization liquid was about 500,000 to 650,000, and the Tg was about -9°C. Next, 4 g of an aqueous ammonia solution (28 wt%), which is a formaldehyde remover, was mixed into the polymerization solution to prepare a polymer composition. Next, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation.

[0126] Example 4. 200 g of purified water and 2.5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0127] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal / cm 3 ) 1 / 2 , Tg: -15°C) 30g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 55g, methyl methacrylate (solubility parameter: 10.1 (cal / cm 3 ) 1 / 2115g of dimethylformamide (Tg: 105°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the introduction rate of the emulsion was controlled to about 85mL / min. FIG. 2 is a photograph of the polymer polymerization liquid obtained through the above process. Through the above process, a polymer polymerization liquid with excellent phase stability without an increase in viscosity was obtained. The molecular weight (Mw) of the prepared polymerization liquid (polymer composition) was about 500,000 to 650,000, and the Tg was about 26.5°C. Next, the polymer composition was mixed with other ingredients as shown in Table 1 below to obtain a mascara formulation.

[0128] Comparative Example 1 200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0129] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 120g, methyl methacrylate (solubility parameter: 10.1 (cal / cm 3 ) 1 / 280g of dimethylformamide (Tg: 105°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added together and polymerization was performed for 24 hours. In this process, the introduction rate of the emulsion was controlled to about 85mL / min. The molecular weight (Mw) of the prepared polymerization liquid (polymer composition) was about 500,000 to 650,000, and the Tg was about -6.2°C. Next, the polymer composition was mixed with other components as shown in Table 1 below to obtain a mascara formulation.

[0130] [Table 1]

[0131] The results of the physical property evaluation for each of the Examples and Comparative Examples are summarized in Table 2 below (in Table 2, the ratio of methanol and the ratio of formaldehyde are based on the polymer composition, and the units are ppm).

[0132] [Table 2]

[0133] Reference example 1. 200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0134] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and acrylic acid (solubility parameter: 13.6 (cal / cm 3 ) 1 / 2 , Tg 105 °C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2, Tg: -50°C) 110g, ethyl methacrylate (solubility parameter: 9.7 (cal / cm 3 ) 1 / 2 80g of ammonium persulfate (Tg: 65°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added and polymerization was performed for 24 hours. In this process, the introduction rate of the emulsion was controlled to about 85mL / min. The Tg of the prepared polymerization liquid (polymer composition) was about -8.6°C. The polymer composition was confirmed in the same manner as in the examples and comparative examples, and methanol was not detected, and the proportion of formaldehyde was about 20.8ppm.

[0135] Reference example 2. 200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0136] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and acrylic acid (solubility parameter: 13.6 (cal / cm 3 ) 1 / 2 , Tg 105 °C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 60g, ethyl methacrylate (solubility parameter: 9.7 (cal / cm 3 ) 1 / 2130g of 1,2-dichloromethane (Tg: 65°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added and polymerization was performed for 24 hours. In this process, the introduction rate of the emulsion was controlled to about 85mL / min. The Tg of the prepared polymerization solution (polymer composition) was about 21.1°C. The ratios of methanol and formaldehyde in the polymer composition were measured in the same manner as in the examples and comparative examples, and methanol was not detected and the ratio of formaldehyde was 21.6ppm. In addition, the results of the bleeding test, powdering test, bleeding test (panel evaluation), and powdering test (panel evaluation) for a mascara formulation obtained in the same formulation as in Example 1, except that the polymer composition was used, were 93.4, 10, B, and D, respectively.

[0137] Reference example 3. 200 g of purified water and 5 g of sodium hydrogen carbonate (saturated with a neutralizing agent) were placed in a reactor 1 equipped with a cooler, a nitrogen injector, a thermometer and a stirrer, and mixed uniformly. The temperature was then raised to 70°C.

[0138] In a separate reactor 2 equipped with a stirrer, 100 g of purified water and acrylic acid (solubility parameter: 13.6 (cal / cm 3 ) 1 / 2 , Tg 105 °C) 10 g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 85g, methyl methacrylate (solubility parameter: 10.1 (cal / cm 3 ) 1 / 2105g of ammonium persulfate (Tg: 105°C), 4g of sodium lauryl sulfate, and 4g of Triton X-405 were added and emulsified. 5% by weight of the emulsion in the reactor 2 was separated and placed in the reactor 1, and 0.5g of an initiator (ammonium persulfate) was added and seed polymerization was performed for 30 minutes. After the seed polymerization, the emulsion remaining in the reactor 2 was introduced into the reactor 1. When the emulsion remaining in the reactor 2 was introduced, 0.5g of an initiator (ammonium persulfate) dissolved in purified water was added and polymerization was performed for 24 hours. In this process, the introduction rate of the emulsion was controlled to about 85mL / min. The Tg of the prepared polymerization solution (polymer composition) was about 18.8°C. The ratios of methanol and formaldehyde in the polymer composition were measured in the same manner as in the examples and comparative examples, and the ratios of methanol and formaldehyde were 19ppm and 38.1ppm, respectively. In addition, the results of the bleeding test, powdering test, bleeding test (panel evaluation), and powdering test (panel evaluation) for a mascara formulation obtained in the same formulation as in Example 1 except that the polymer composition was used were 95.5, 14, A, and D, respectively.

[0139] Reference example 4. In a reactor equipped with a condenser, nitrogen injector, thermometer, and stirrer, 300 g of purified water and 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal / cm 3 ) 1 / 2 , Tg: -15°C) 30g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 90g, ethyl methacrylate (solubility parameter: 9.7 (cal / cm 3 ) 1 / 2 80g of dimethylformamide (Tg: 65°C), 4g of sodium lauryl sulfate, 4g of Triton X-405, and 2.5g of sodium bicarbonate saturated with a neutralizer were added and emulsified, and the temperature was raised to 70°C. Then, 1g of an initiator (ammonium persulfate) was added and polymerization was carried out for 24 hours. The Tg of the polymer solution produced was about -9°C. Figure 3 is a photograph of the polymer solution obtained through the above process.

[0140] Reference example 5. In a reactor equipped with a condenser, nitrogen injector, thermometer, and stirrer, 300 g of purified water and 2-hydroxyethyl acrylate (solubility parameter: 14.1 (cal / cm 3 ) 1 / 2 , Tg: -15°C) 30g, 2-ethylhexyl acrylate (solubility parameter: 8.8 (cal / cm 3 ) 1 / 2 , Tg: -50°C) 55g, methyl methacrylate (solubility parameter: 10.1 (cal / cm 3 ) 1 / 2 115g of dimethylformamide (Tg: 105°C), 4g of sodium lauryl sulfate, 4g of Triton X-405, and 2.5g of sodium bicarbonate saturated with a neutralizer were added and emulsified, and the temperature was raised to 70°C. Then, 1g of an initiator (ammonium persulfate) was added and polymerization was carried out for 24 hours. The Tg of the polymer solution produced was about 26.5°C. Figure 4 is a photograph of the polymer solution obtained through the above process.

Claims

1. The solubility parameter of a single polymer is 11.0 (cal / cm ３ ) １／２ The solubility parameter of the polymerized unit of the first monomer and the single polymer is 11.0 (cal / cm ３ ) １／２ and a polymer comprising polymerized units of a second monomer, the first monomer comprises a hydroxy group-containing monomer or an acidic monomer; The second monomer is represented by the following formula 3: 【Chemistry 1】 (wherein Q is hydrogen or an alkyl group, and B is a straight or branched alkyl group having two or more carbon atoms, an alicyclic hydrocarbon group, or an aromatic substituent group), the polymerized units of the second monomer include polymerized units of a monomer (A) having a glass transition temperature of 20° C. or higher and polymerized units of a monomer (B) having a glass transition temperature of lower than 20° C.; a weight ratio (A / B) of the monomer (A) polymerization units to the monomer (B) polymerization units is within a range of 0.6 to 0.95; In the polymer, a ratio of the polymerization units of the first monomer is within a range of 1 to 40% by weight, the polymer comprises 150 to 4000 parts by weight of polymerized units of a second monomer per 100 parts by weight of polymerized units of the first monomer; A polymer composition, wherein the polymer has a glass transition temperature in the range of -30°C to 5°C.

2. 2. The polymer composition according to claim 1, wherein the proportion of methanol is 30 ppm or less.

3. 2. The polymer composition according to claim 1, wherein the proportion of formaldehyde is 30 ppm or less.

4. 10. The polymeric composition of claim 1, wherein the polymer does not contain polymerized units of a methanol-producing monomer.

5. 5. The polymeric composition of claim 4, wherein the methanol-producing monomer is methyl (meth)acrylate.

6. 2. The polymer composition according to claim 1, wherein the first monomer has a glass transition temperature in the range of -40°C to 400°C.

7. 2. The polymer composition according to claim 1, wherein the polymer has a weight average molecular weight in the range of 100,000 to 2,000,000.

8. The polymeric composition of claim 1 , wherein the polymer is a seed emulsion polymer.

9. The polymeric composition of claim 1 further comprising a formaldehyde scavenger.

10. A first stage of seeded emulsion polymerization of a reaction solution including a monomer mixture, an aqueous solvent, and a surfactant; a second step of carrying out emulsion polymerization while introducing a reaction solution containing a monomer mixture into the seed emulsion polymer of the first step, thereby growing the seeds generated in the first step; The monomer mixtures in the first and second steps each have a solubility parameter of 11.0 (cal / cm ３ ) １／２ The solubility parameter of the first monomer and the single polymer is 11.0 (cal / cm ３ ) １／２ a second monomer that is less than A method for producing a polymer composition, comprising the steps of: a ratio of the first monomer in the monomer mixture in the first and second steps is within a range of 4 to 40% by weight; and the monomer mixture contains 150 to 4000 parts by weight of the second monomer per 100 parts by weight of the first monomer; the first monomer comprises a hydroxy group-containing monomer or an acidic monomer; The second monomer is represented by the following formula 3: 【Chemistry 2】 (In Chemical Formula 3, Q is hydrogen or an alkyl group, and B is a linear or branched alkyl group having two or more carbon atoms, an alicyclic hydrocarbon group, or an aromatic substituent group). the polymerized units of the second monomer include polymerized units of a monomer (A) having a glass transition temperature of 20° C. or higher and polymerized units of a monomer (B) having a glass transition temperature of lower than 20° C.; a weight ratio (A / B) of the monomer (A) polymerization units to the monomer (B) polymerization units is within a range of 0.6 to 0.95; The method wherein the glass transition temperature of the polymer is within the range of -30°C to 5°C.

11. The method for producing a polymer composition according to claim 10, further comprising the step of separating a part of a total reaction solution prepared by mixing a monomer mixture, an aqueous solvent and a surfactant before the first step, to obtain a reaction solution for the first step.

12. The method of claim 10, further comprising the step of mixing the polymer from the second step with a formaldehyde scavenger.

13. A film-forming agent comprising the polymeric composition of claim 1.

14. A cosmetic composition comprising the polymeric composition of claim 1 or the film former of claim 13.

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